A3A′3Zn6Te4O24 (A = Na, A′ = Rare Earth) Garnets: A‑Site Ordered Noncentrosymmetric Structure, Photoluminescence, and Na-Ion Conductivity

• Published in: Inorganic chemistry 2021-12, Vol.60 (23), p.18168-18177
• Main Authors: Fang, Zhilin, Jiang, Pengfei, Avdeev, Maxim, Wei, Hengwei, Wang, Rong, Jiang, Xingxing, Yang, Tao
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.1c02815

A large number of oxides that adopt the centrosymmetric (CS) garnet-type structure (space group Ia3̅d) have been widely studied as promising magnetic and host materials. Hitherto, no noncentrosymmetric (NCS) garnet has been reported yet, and a strategy to NCS garnet design is therefore significant for expanding the application scope. Herein, for the series A3A′3Zn6Te4O24 (A = Na, A′ = La, Eu, Nd, Y, and Lu), we demonstrated that the structural symmetry evolution from CS Ia3̅d (A′ = La) to NCS I4122 (A′ = Eu, Nd, Y, and Lu) could be achieved due to the A-site cationic ordering-driven inversion symmetry breaking. Na3A′3Zn6Te4O24 (A′ = rare earth) are the first garnets that possess NCS structures with A-site cationic ordering. Diffuse reflectance spectra and theoretic calculations demonstrated that all these NCS garnets are indirect semiconductors. Moreover, their potential applications as host materials for red phosphors and Na-ion conductors were also investigated in detail, which firmly confirmed the NCS structure and A-site cationic ordering. Our findings have paved the way to design NCS or even polar garnets that show intriguing functional properties, such as ferroelectricity, multiferroicity, and second harmonic generation.